Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/10—Preparations for permanently dyeing the hair
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
  • C07C211/53—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a hydrocarbon radical substituted by amino groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
  • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
  • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
  • C07C215/18—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with hydroxy groups and at least two amino groups bound to the carbon skeleton

Definitions

• the present invention relates to a new process for preparing N,N'-tetrasubstituted aliphatic ⁇ , ⁇ -diamines, to the new compounds consisting of N,N'-bis( ⁇ -hydroxyethyl) -N,N'-bis(4'-aminophenyl)-1,3-diamino-2-propanol and to N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, their addition salts with acids and their use in oxidation hair dyeing.
• the process for preparing these compounds consists essentially in performing, in a first stage, a reaction of tosylation of p-acetaminoaniline to obtain N-acetyl-N'-tosyl-para-phenylenediamine, followed, in a second stage, by a condensation of a dihalohydrocarbon with an alkali metal or alkaline-earth metal salt of N-acetyl-N'-tosyl-para-phenylenediamine, in carrying out, in a third stage, a selective hydrolysis of the tosyl groups of the N,N'-bistosyl-N,N'-bis(4'-acetamidophenyl) alkylenediamine obtained during the second stage. This hydrolysis is carried out with the aid of cold sulphuric acid and produces N,N'-bis(4'-acetamidophenyl)alkylenediamine.
• the fourth stage of this previous process is an alkylation or a hydroxyalkylation or aminoalkylation of the secondary amine functional groups.
• the fifth stage consists in performing the hydrolysis of the acetamido functional group by reaction with hydrochloric acid with heating.
• R denotes a C 1 -C 4 alkyl, C 2 -C 4 hydroxy alkyl or C 2 -C 4 aminoalkyl radical
• X denotes a halogen atom, preferably chlorine or bromine
• R 1 denotes a hydrogen or halogen atom or a C 1 -C 4 alkyl radical
• Y denotes the group --(CH 2 ) n --with n having a value from 0 to 8, or else the group --(CH 2 ) n' --CHOH --(CH 2 ) n --where n'--is an integer from 0 to 4.
• a dihalogenated hydrocarbon of formula (II) is condensed with an N-substituted aniline (I) in a polar solvent and in the presence of a basic compound;
• the polar solvent is preferably water.
• the basic compound is employed in sufficient quantities to trap the hydrogen halide acid formed and it is preferably chosen from alkali metal or alkaline-earth metal carbonates.
• the reaction temperature preferably varies between 50° C. and the reflux temperature of the reaction mixture.
• the nitrosation reaction is carried out essentially by reaction with a sodium nitrite/hydrochloric acid mixture in water, at a temperature below 10° C., preferably between -2° and +5° C.
• the reduction applied in the third stage of the process is performed in an ethanolic medium in the presence of ammonium chloride and zinc at the reflux temperature of the solvent.
• the reduction can also be carried out by a catalytic route in a solvent consisting of a lower C 1 -C 4 alcohol, a water-alcohol mixture, ethyl acetate or tetrahydrofuran, using nickel, platinum or palladium on charcoal as a catalyst
• the reduction can also be performed under hydrogen pressure at a temperature of between 20° C. and 100° C. and at a pressure which is preferably below 10 bars (1000 kPa).
• Another subject of the invention consists of N,N'-bis( ⁇ -hydroxyethyl)-N,N'-bis(4'-aminophenyl) -1,3-diamino-2-propanol and of N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl) ethylenediamine and their addition salts with acids.
• Another subject of the invention consists of the use of one or both of these new compounds or of their salts as an oxidation dye precursor of the para type in oxidation dyeing compositions for hair. These compounds produce dyes which are stable to washing, to light and to inclement weather, and are satisfactorily innocuous.
• the compound defined above may be employed in combination with tinters or couplers chosen, in particular, from phenols, meta-diphenols, meta-aminophenols, meta-phenylenediamines, mono- or polyhydroxylated derivatives of naphthalene and of aminonaphthalene, pyrazolones, benzomorpholines, heterocyclic couplers derived from pyridine, sesamol and its derivatives.
• tinters or couplers chosen, in particular, from phenols, meta-diphenols, meta-aminophenols, meta-phenylenediamines, mono- or polyhydroxylated derivatives of naphthalene and of aminonaphthalene, pyrazolones, benzomorpholines, heterocyclic couplers derived from pyridine, sesamol and its derivatives.
• the concentration of the dye precursor defined above is generally between 0.05 and 12% and preferably between 0.1 and 5% by weight.
• couplers are employed in concentrations of between 0.05 and 10% by weight relative to the total weight of the composition.
• the pH of these compositions is preferably alkaline and, in particular, it is between 8 and 11.
• compositions contain the dye precursor in a suitable medium for dyeing, known per se, which may be more or less thickened or jelled liquid, an emulsion, a foam or any other form which is suitable for dyeing.
• This medium is preferably aqueous and may consist of water or a mixture of water and an organic solvent such as ethyl alcohol, propyl or isopropyl alcohol, tertbutyl alcohol, benzyl or phenylethyl alcohol, ethylene glycol, polyethylene glycols, ethylene glycol monomethyl, monoethyl or monobutyl ethers, ethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol and dipropylene glycol monomethyl ethers or methyl lactate.
• an organic solvent such as ethyl alcohol, propyl or isopropyl alcohol, tertbutyl alcohol, benzyl or phenylethyl alcohol, ethylene glycol, polyethylene glycols, ethylene glycol monomethyl, monoethyl or monobutyl ethers, ethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol and dipropylene glycol
• compositions may contain any other adjuvant usually employed in dyeing keratinous fibres, in particular anionic, cationic, nonionic or amphoteric surface-active agents or mixtures thereof, thickening agents, perfumes, sequestering agents, film-forming agents, processing agents, dispersing agents, conditioning agents, preserving agents, opacifying agents, agents for swelling keratinous fibres, and the like.
• adjuvant usually employed in dyeing keratinous fibres in particular anionic, cationic, nonionic or amphoteric surface-active agents or mixtures thereof, thickening agents, perfumes, sequestering agents, film-forming agents, processing agents, dispersing agents, conditioning agents, preserving agents, opacifying agents, agents for swelling keratinous fibres, and the like.
• compositions in accordance with the invention may also contain direct dyes intended to tint the colour, such as the nitro derivatives of the benzene series and anthraquinone, naphthaquinone or azo dyes.
• the process for dyeing keratinous fibres, in particular human hair consists in applying to these fibres a composition containing at least one dye precursor defined above in a sufficient quantity to dye them.
• This composition is preferably mixed beforehand with an oxidizing agent such as hydrogen peroxide or a persalt, with a view to developing the colour.
• composition is kept in contact with the fibres for a period of 5 minutes to 1 hour and a rinsing is then carried out, followed optionally by washing, rinsing again and drying.
• the expected product crystallizes after cooling and neutralizing with 50 ml of concentrated hydrochloric acid.
• the product obtained is recrystallized from isopropyl alcohol. 238 g of the expected product are obtained. It melts at 120° C.
• a solution of 1.14 moles (78.7 g) of sodium nitrite in 150 ml of water is added dropwise at between 0° C. and 5° C. to a solution of 0.5 moles (165.2 g) of N,N'-bis( ⁇ -hydroxyethyl)-N,N'-bis(phenyl) -1,3-diamino-2propanol, prepared in the preceding stage, 290 ml of concentrated hydrochloric acid and 900 g of ice. After the end of addition stirring is continued for 1 h 30 min. The reaction mixture is neutralized by adding 300 ml of 20% strength aqueous ammonia at 10° C. After filtering off, the product obtained is made into a paste with water. It can be employed moist for the following stage.
• Zinc is removed by filtering the reaction mixture hot and the expected product is precipitated by adding 340 ml of a solution of hydrochloric acid in absolute ethanol (7.5 N) to the filtrate. 234 g of expected product are obtained after drying by adding ethyl ether.
• the product is recrystallized from absolute ethanol.
• a solution of 0.106 moles (7.3 g) of sodium nitrite in 17 ml of water is added dropwise at 0° C. to a solution of 0.05 moles (18.5 g) of N,N'-bis(ethyl)-N,N'-bis(3'-methylphenyl)ethylenediamine in the form of dihydrochloride prepared in the preceding stage, of 20 ml of concentrated hydrochloric acid and 105 g of ice. After the end of addition the stirring is continued for 30 minutes. The hydrochloride of the expected product crystallizes.
• the expected product precipitates after addition of 15 ml of 20% strength aqueous ammonia to a suspension of the product obtained in 200 ml of water. Recrystallized from 200 ml of 96° ethanol, it melts at 157° C.
• Zinc is removed by filtering the reaction mixture hot.
• the expected product is obtained after adding an ethanolic solution of hydrochloric acid and evaporating to dryness.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Veterinary Medicine (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)
• Coloring (AREA)

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Cited By (9)

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Citations (9)

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• 1988
  • 1988-09-06 FR FR8811634A patent/FR2636062B1/fr not_active Expired - Fee Related
• 1989
  • 1989-09-01 EP EP89402384A patent/EP0358550B1/fr not_active Expired - Lifetime
  • 1989-09-01 ES ES89402384T patent/ES2062067T3/es not_active Expired - Lifetime
  • 1989-09-01 DE DE68914221T patent/DE68914221T2/de not_active Expired - Lifetime
  • 1989-09-01 AT AT89402384T patent/ATE103586T1/de not_active IP Right Cessation
  • 1989-09-05 JP JP1228483A patent/JP2916173B2/ja not_active Expired - Fee Related
  • 1989-09-06 CA CA000610449A patent/CA1327608C/fr not_active Expired - Fee Related
  • 1989-09-06 US US07/403,390 patent/US5114429A/en not_active Expired - Lifetime
• 1998
  • 1998-11-18 JP JP10327926A patent/JPH11292830A/ja active Pending

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